CA1288372C - Amphiphilic phase behavior separation of carboxylic acids/hydrocarbon mixtures in recovery of oil from tar sands or the like - Google Patents
Amphiphilic phase behavior separation of carboxylic acids/hydrocarbon mixtures in recovery of oil from tar sands or the likeInfo
- Publication number
- CA1288372C CA1288372C CA000551228A CA551228A CA1288372C CA 1288372 C CA1288372 C CA 1288372C CA 000551228 A CA000551228 A CA 000551228A CA 551228 A CA551228 A CA 551228A CA 1288372 C CA1288372 C CA 1288372C
- Authority
- CA
- Canada
- Prior art keywords
- acid
- alcohol
- recited
- acids
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 150000001735 carboxylic acids Chemical class 0.000 title claims abstract description 32
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 29
- 238000000926 separation method Methods 0.000 title claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 22
- 238000011084 recovery Methods 0.000 title abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 160
- 230000008569 process Effects 0.000 claims abstract description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000010426 asphalt Substances 0.000 claims abstract description 66
- 239000012267 brine Substances 0.000 claims abstract description 49
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 48
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 35
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010779 crude oil Substances 0.000 claims abstract description 22
- 239000003921 oil Substances 0.000 claims abstract description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000005191 phase separation Methods 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 43
- 150000007513 acids Chemical class 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 230000005484 gravity Effects 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000295 fuel oil Substances 0.000 claims description 7
- 229960004232 linoleic acid Drugs 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 6
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 claims description 5
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 4
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 4
- 229940098330 gamma linoleic acid Drugs 0.000 claims description 4
- VZCCETWTMQHEPK-UHFFFAOYSA-N gamma-Linolensaeure Natural products CCCCCC=CCC=CCC=CCCCCC(O)=O VZCCETWTMQHEPK-UHFFFAOYSA-N 0.000 claims description 4
- VZCCETWTMQHEPK-QNEBEIHSSA-N gamma-linolenic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCC(O)=O VZCCETWTMQHEPK-QNEBEIHSSA-N 0.000 claims description 4
- 229960004488 linolenic acid Drugs 0.000 claims description 4
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 235000021353 Lignoceric acid Nutrition 0.000 claims description 3
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- CNVZJPUDSLNTQU-UHFFFAOYSA-N Petroselaidic acid Natural products CCCCCCCCCCCC=CCCCCC(O)=O CNVZJPUDSLNTQU-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 claims description 3
- 229940087675 benzilic acid Drugs 0.000 claims description 3
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- CNVZJPUDSLNTQU-OUKQBFOZSA-N petroselaidic acid Chemical compound CCCCCCCCCCC\C=C\CCCCC(O)=O CNVZJPUDSLNTQU-OUKQBFOZSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 3
- 150000003566 thiocarboxylic acids Chemical class 0.000 claims description 3
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 6
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims 3
- 235000021360 Myristic acid Nutrition 0.000 claims 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims 3
- 238000010438 heat treatment Methods 0.000 claims 3
- SELIRUAKCBWGGE-UHFFFAOYSA-N hexadecanoic acid;octadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O SELIRUAKCBWGGE-UHFFFAOYSA-N 0.000 claims 3
- 235000020778 linoleic acid Nutrition 0.000 claims 3
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims 3
- 239000003849 aromatic solvent Substances 0.000 claims 2
- 125000004429 atom Chemical group 0.000 claims 2
- 230000003247 decreasing effect Effects 0.000 claims 2
- 239000002803 fossil fuel Substances 0.000 claims 2
- 239000003209 petroleum derivative Substances 0.000 claims 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 47
- 229930195729 fatty acid Natural products 0.000 abstract description 47
- 239000000194 fatty acid Substances 0.000 abstract description 47
- 150000004665 fatty acids Chemical class 0.000 abstract description 46
- 239000002904 solvent Substances 0.000 abstract description 31
- 238000004821 distillation Methods 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 10
- 239000003085 diluting agent Substances 0.000 abstract description 8
- 238000002347 injection Methods 0.000 abstract description 7
- 239000007924 injection Substances 0.000 abstract description 7
- 238000012545 processing Methods 0.000 abstract description 7
- 239000012141 concentrate Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 28
- 235000019198 oils Nutrition 0.000 description 14
- 239000011269 tar Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000007614 solvation Methods 0.000 description 7
- 239000011275 tar sand Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- 238000013459 approach Methods 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 238000005065 mining Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- -1 fatty acid salts Chemical class 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019485 Safflower oil Nutrition 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 235000005713 safflower oil Nutrition 0.000 description 2
- 239000003813 safflower oil Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 101100478173 Drosophila melanogaster spen gene Proteins 0.000 description 1
- 101100513476 Mus musculus Spen gene Proteins 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 241000708948 Solva Species 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004391 petroleum recovery Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/34—Arrangements for separating materials produced by the well
- E21B43/40—Separation associated with re-injection of separated materials
Abstract
ABSTRACT OF THE DISCLOSURE
There is disclosed a process of oil recovery from tar sands or separation of hydrocarbons from a solid or viscous bitumen source wherein carboxylic acids or carboxylic acid mixtures are utilized as a solvent or diluent and are mixed with heavy crude oil, injected into an oil reservoir or mixed with tar sands in a surface vessel to reduce the viscosity of the crude oil and to increase the mobility of the oil. The process is characterized by the use of an amphiphilic phase separation induced by injection of isopropanol or other alcohol to facilitate the recovery of carboxylic acid diluent from the bitumen product, and another phase separation step may be employed to separate the carboxylic acid component from the alcohol. Sodium chloride or other brine solution is usually mixed with the alcohol and many embodiments combine a light hydro-carbon such as heptane with the carboxylic acid as an additional solvent. Carboxylic acids in the form of fatty acids with from 8 to 20 carbon atoms are preferred. Distillation may be employed to separate the alcohol from the brine solution or to concentrate the alcohol for recycling. All the processing chemicals may be recycled in the process with the exception of the light hydrocarbons, which may or may not be separated from the product stream in later conventional processing.
There is disclosed a process of oil recovery from tar sands or separation of hydrocarbons from a solid or viscous bitumen source wherein carboxylic acids or carboxylic acid mixtures are utilized as a solvent or diluent and are mixed with heavy crude oil, injected into an oil reservoir or mixed with tar sands in a surface vessel to reduce the viscosity of the crude oil and to increase the mobility of the oil. The process is characterized by the use of an amphiphilic phase separation induced by injection of isopropanol or other alcohol to facilitate the recovery of carboxylic acid diluent from the bitumen product, and another phase separation step may be employed to separate the carboxylic acid component from the alcohol. Sodium chloride or other brine solution is usually mixed with the alcohol and many embodiments combine a light hydro-carbon such as heptane with the carboxylic acid as an additional solvent. Carboxylic acids in the form of fatty acids with from 8 to 20 carbon atoms are preferred. Distillation may be employed to separate the alcohol from the brine solution or to concentrate the alcohol for recycling. All the processing chemicals may be recycled in the process with the exception of the light hydrocarbons, which may or may not be separated from the product stream in later conventional processing.
Description
7.~
AMPHIPHILIC PHASE BE~AVIOR SEPARATION
OF CARBOXYLIC ACIDS/HYDROCARBON MIXTURES IN RECOVERY
OE' OIL FROM TAR SANDS OR THE LIKE
The present invention rela-tes primarily to heavy oil and bitumen recovery systems using carboxylic acids, (and in most cases also l;ght hydrocarbons) as extraction solvents for recovering the oil or bitumen components and is particularly characterized by the efficient recovery of the carboxylic acid components for recycle purposes. The molecules of selected acids used will normally contain from 8 to 20 carbon atoms.
This recovery is accomplished by a low-energy, alcohol-induced amphiphilic phase separation procedure. It also may find application in fractionating light hydrocarbon components from heavy hydrocarbon components in the oil or bitumen. For rea-sons of economy, carboxylic acids within the group known as fatty acids will genera]ly be employed; fatty acids is a -term given to monobasic aliphatic carbo~ylic acids.
There are two basic approaches to recovering heavy oil or bitumen. The tar sand resource may be mined and trans-ported to a process plant where the bitumen is extracted using solvents, or the separation may be accomplished in situ. In situ processes have a great deal in common with secondary or enhanced recovery of conventional lighter crude oil.
Conventional ligh-t crude oil is produced from the oil-bearing formations by drilling wells down into the forma-tion. The oil usually is driven from the ~ormation into the wells (production wells) by energy stored in the formation, such as the pressure of natural gas. When this natural energy of the Eormation is expended or, as in the case of most tar sands if it never was present, then energy must be injec-ted into the formation (via injection wells) in order to stimulate production. A third essential element for a successful in situ process is a means of communication between the injection ~, 7 3.2~33'^~
wells and the production wells.
In the case of heavy oil tar sand in situ production, solvating chemical agents and/or steam are often used as the injection fluid in -the injection wells. ~Iydraulic fracturing techniques are usually used to generate communication between injection and production wells. The solvating agent normally would be an admixture of ei-ther a light hydrocarbon diluent, an emulsifying agent with water, or in the case of the present invention a carboxylic acid admixture which may also include a light hydrocarbon.
The alternative to an in situ processing scheme is to mine the tar sands, transport them from their place in the formation to a processing plant, extract the bitumen value, and dispose of the waste sand. The emphasis in the following description is on the mined tar sands approach, but in situ processing is not excluded.
Shaft mining of tar sands is considered impractical because of economic considerations, but could theoretically be employed. There are two approaches to the open pit mining of tar sands. The first is to use a few mining units of custom design, which will necessarily be very expensive. E;or instance, large units which have been considered are bucket wheel excavators, dredges ( both hydraulic and bucket ladder) and super-sized draglines. The other approach is to use a multiplici-ty of smaller mining units of conventional design and relatively much lower unit costs. For example, scrapers and truck-and-shovel operations may be considered. Each method has advantages for par-ticular situations.
The solvent extraction processes used in conjunction with surface-minecl tar sand opera-tions vary primarily with respect to contacting-device used to extract the solvated bitumen from the sand particles and with respect to the means of recovery of the solvating agent for recycle purposes. The traditional method for separation of solverlt 8~3~
from crude oil is distillation which is energy intensive and often renders a process economically and ecologically unattractive. Losses of solvent associated with the spent sand may also decrease the economic feasibility of the process. The present invention contemplates the use of amphiphilic phase behavior to bring about a low energy requirement for recovery of the solvent and may utilize a wa-ter enhanced washing scheme in order to minimize solvent losses to the spen t s and .
In U. S. Patent No. 4,480,691 entitled "Recycle~ Fat-ty Acid Crude Petroleum Recovery Process" issued to ~lerter et al. on November 6, 1984, there is described a method of recovering crude oil from materials such as tar sands, kerogen or the like wherein the crude oil source is treated with a fatty acid to produce a solvated crude oil mixture of reduced viscosity. The fatty acid in this mixture is then saponified by re~cting it with an aqueous base such as an alkali metal hydroxide to separate the solvated mixture into petroleum crude and an acid soap which will Inigrate into the aqueous phase.
The petroleum crude is separated from the aqueous soap solution and subsequently the fatty acid is recovered by a desaponification s-tep which is conducted in the presence of an acid. Car~onic acid can be generated for the desaponifying step by injecting high pressure carbon dioxide with the desaponification treating vessel. Additional refining can take place by other separation or filtration steps.
In that Herter process, the efficiency of recovery of the fatty acid solvent for further use represents a prime economic consideration.
~lowever, it has been found that as a result of emulsification in the saponification portion of the process, the economic practicality of solvent recovery used in the Herter process is limited. There has been some progress to improve the Herter process by reducing or eliminating emulsification in the saponification step.
3837~
Although -there have been numerous prior applica-tion of carboxylic acids and especially fatty acids in enhanced oil recovery, these applications use the fatty acid salts or soaps and their derivatives as surfactants, while the Herter process and related processes use a free carboxylic acid as a solvating chemical agent.
An economically important portion of the Herter process and tar sand processes generally concerns the recovery of fatty acid or other solvent from the solvated hydrocarbon mixture.
Fatty acids tend to form azeotropes with most desired petroleum fractions, making the refining of crude oil containing fatty acids much more difficult. Separation of fatty acids from such a mixture by a method other than distillation is thus highly desirable. The approach used in Herter and related processes is saponification oE
the solvated mixture with an aqueous base, followed by migration of the resulting soap into the aqueous phase, and then desaponification of the aqueous phase to regenerate the fatty acid.
The present invention is an improvement (over the Herter and related processes) utilizing amphiphilic phase behavior for carboxylic acid recovery and thereby eliminating the need for both the saponifi-cation and desaponification steps of the Herter process. The present invention may be applicable to separations of carboxylic acids and hydrocarbon mixtures in t'ne fractionations of heavy oil or bitumen into asphaltene and malthene components. When the bitumen or oil feed material is other than tar sand, the invention may be used in cleaning up oil spills, reducing the viscosity of heavy oil or bitumen for transportation by pipeline, the reclaiming of used oil, and the recovery of sur~actants from oil admixtures.
Prior patents in other technologies such as Donald V. Julian, "~ec~ es Patent No. 3,691,211, Sept. 2, 1972, -to Procter & Gamble Co. have suggested phase separation to recover acid process material for 3 7;?d recycling, but the actual process employed has no applicability to crude oil recovery processes as provided by the present invention.
The present invention makes use of carboxylic acids (with 8 to 20 carbon atoms) or carboxylic acid mixtures as a solvent or diluent which is mixed wi-th an oil, injected into an oil reservoir, or mixed with tar sands in a surface vessel -to reduce the viscosity of the crude oil and to increase the mobility of the oil. This feature is also found in the Herter process. However, the present invention differs in its unique process for recovery of carboxylic acid diluent by amphiphilic phase separation induced by alcohol injection whereas Herter et al proposed the separation of fatty acid from a petroleum mixture by saponification of the solvated mixture with an aqueous base, followed by migration of the resulting soap into the aqueous phase, and then desaponification of the aqueous phase to regenerate the fatty acid. Specifically, the present invention contemplates using a lower alcohol containing from l to 8 carbon atoms as an amphiphilic cosolvent with the carboxylic acids and preferably employs isopropanol or n-butanol for this purpose. An aqueous brine solution may also be used to enhance the amphiphilic phase separations. Acids used in accordance with the present inven-tion are usually straight chain carboxylic acids containing between 8 and 18 carbon atoms. The invention may alternatively make use of naturally occurring saturated carboxylic acids with carbon chain lengths between 12 and 20, as well as unsaturated carboxylic acids with a carbon chain length of up to 20 a-toms. These unsaturated acids have lower melting points than the corresponding saturated acids and remain liquids at lower temperatures than the saturated fatty acids, making them attractive for use in the process. Three common unsaturated fatty acids which can be used in connection with the presen-t invention are oleic acid, linoleic acid, and linolenic acid. ~iixtures of fatty acids or acids containing irnpurities such as rosin acids can also be employed.
. ~
~ 2~3~3~7~
It is contempla-ted that a combination of the present invention and a Herter acid regeneration process arranged in series could prove advantageous. The present invention would bring about a rough cut of the separation of carboxylic acids from the many hydrocarbons and the Herter process would accomplish a higher purity separation when this i5 desired.
After the carboxylic acid components are separated from the bitumen-derived components according to the present p.rocess there is still a need to individually separate the acid components and the alcohol-water components for recycling pur-poses.
The alcohol-water and acid components may be separa-ted in a straightforward manner by distillation techniques.
Such conventional techniques are suitable for this separation process because, unlike the separation of the carboxylic acid and bitumen product, separation of the alcohol and water from the carboxylic acids is not difficult or especially energy ,.
in-tensive; thus with conventional energy conservation proce-dures such distillation can be cost effective.
According to the invention a different separation procedure may be employed to achieve better economy in some cases. This involves mixing process water with the carboxylic acid and alcohol admixture to achieve water overdosing which shifts the phase equilibrium and allows gravity separation of the carboxylic acids component. Following this step, only very simple and efficient distillation methods may be used to separate the alcohol from its water or brine diluent. Alcohol does not need to be obtained in a pure form Erom this process and may contain significant amounts of water because the pro-cess input normal alcohol-water composition is below the 6g370-7 azeotrope composition. This significantly reduces the energy requirements of the ~alcohol concentrating step.
In addition to providing the above described features and advantages it is an object oE the present invention to provide a ~ 6a -~r ~: ` .".
34~
process for separation of carboxylic acid admixtures from hydrocarbons useful in processes such as the recovery of oil from tar sands or the like wherein an adrnixture of carboxylic acid usually also containing light hydrocarbons such as heptane is combined with a bitumen source as an extraction solvent after which amphiphilic phase behavior separa-tion of the carboxylic acid component is achieved by introducing an alcohol-water or alcohol brine solution into the mixture.
I t is another ob ject of the present invention to carry out the above process utilizing carboxylic acids having 8 to 20 carbon atoms and to gravity separate the carboxylic acid and alcohol-water component for recovery of the acid and alcohol components for recycling use .
It is still another object of the present invention to provide a process as described above wherein separation of the carboxylic acids is achieved in part by water overdosing the admixture resulting from the process and thereafter gravity separating the carboxylic acid from the alcohol-water component.
Other objects and advantages of the invention ~ill be apparent from consideration of the following description in conjunction with the appended drawings in which;
FIGURE 1 is a schematic diagram showing apparatus and process employed to carry out the methods according to the present invention;
FIGURE 2 is a schematic diagram showing an alterna-tive apparatus and process including water overdose phase separation for recovery of recycle acid from the acid-alcohol-water process stream; and FIGURE 3 is a schematic flow chart diagram of a process according to the invention showing more extensive recycling of process chemicals for environmental prolection.
Referring now to the drawings, FIGURE 1 shows a basic preferred process and apparatus therefor according to the invention. Bitumen source material is input through a channel 11 suitable for the solid or semi-solid tar sands or other bitumen source material. Solvent input 17 is connected to lines 13 and 15 for input of fatty acid and light hydrocarbon solvents. A holding tank 19 for recycled fatty acid also feeds the solvent input 17. Line 21 supplies recycled fatty acid to holding tank 19 from a source later to be described.
A solvation contactor 23 of known construction is provided to receive bitumen source material through channel 11 and solvent liquids through line 17. Solvation contactor apparatus of suitable form is shown in U.S. Pat. 4,311,561 dated Jan. 19, 1982, to Larry W. Hastings entitled "Apparatus for Extracting Bitumen from Tar Sand."
Other apparatus for contacting tar sand or other bitumen source with solvent to efficiently produce solvated bitumen is referred to in the above patent. Solid waste from the solvation contactor 23 exits through channel 25. In some cases the sand from solvation contactor 23 may be washed or otherwise processed and usefully employed in the production of glass or as a raw material in some other manufacturing process. Treatment of the waste from the solvation contactor 25 does not, however, form a part of the present invention.
Solvated bitumen is transferred through line 27 to a holding tank 2~. Alcohol-water mixture utilized in the process is stored in holding ~ank 31. Tank 31 is supplied through line 33 from recycling apparatus to be later described. At least a small quantity of alcohol ( typically isopropyl alcohol) will be lost in the process and must be made up. Tank 35 contains the make up alcohol.
A blender 51 has a supply line 49 which is connnected to receive solva ted bitumen through line 37, alcohol-water through line 41 and makeup alcohol through line 45; pumps 39, 43 and variable delivery pump 47 serve to produce and control the flow of liquids to blender 51.
It will be understood that while pumps are shown in particular locations in the diagram of FIGURE 1, it is basically a schematic diagram and actual pump locations and flow line connections would 8~
be determined in accordance with conventional techniques of chemical plant design. The same is true of FIGURE 2. Neither the number or the location o-E the pumps illustrated is critical to the design of the appar~tus for carrying out the process of the invention.
While tank 31 is designated an alcohol-water tank, in many cases the process will be more effective with brine rather than water being admi~ed with the alcohol. In other words the water of tank 31 may have and usually will have sodium chloride or a similar salt in solution.
The alcohol content of the alcohol-brine solution fed to blender 51 with the solvated bitumen may be varied by opera-tion of the variable delivery pump 47. Other means of a con-ventional type may be employed to control the materials propor-tions for blender 51. Blender 51 is conven-tional liquid blend-ing apparatus employing mechanical agitation or other suitable mechanism for attaining a homogeneous mixture. A primary phase settler 55 is fed directly from blender 51 ~hrough line 53. In settler 55 a phase formation takes place resulting in gravity separation of a lower heavy hydrocarbon phase containing small or insignificant amounts of alcohol, brine, and acid process chemicals. Other means for separating liquids of different density could be used in place of conventional set-tler 55. The heavy hydrocarbon phase is removed through line 59 and pumped or otherwise transported to product storage tank 61.
The eeficiency of the process may be i.mproved if the lower phase in settler tanlc 55 is heated to Erom ~0 C. to 50 C. or higher temperatures and an optional heater 57 may be employed for that purpose. The upper phase (or phases) of primary settler 55 contains virtually all process constituen-ts 1"
~ 3~ 69370-7 except for the bitumen-derived hydrocarbon product and light hydrocarbon diluent, and the remaining upper phase constituents are fed through line 63 by means of pump 65 to a boi:ler 67.
Boiler 67 feeds a condenser 71 through line 69 ~ 9a -. ",,~ .
~ ~13t'33~.
whereby an alcohol-rich vapor phase is condensed and transported through line ~i3 by pump 75 to alcohol-water tank 31. In some cases it may be necessary or desirable to replace boiler 67 and condenser 71 with a distillation column of two or more stages for higher concen-tration of alcohol in line 73.
The liquid phase from boiler 67 is passed into line 77; after being cooled by fan cooler 79 it is delivered by pump 81 to secondary phase settler 83.
After reduction of the alcohol concentration in line 77 phase separation takes place in secondary settler 83 wherein the upper phase is the fatty acid constituent which is delivered through line 89 by pump 91 to fatty acid hold tank 93, where it may be controlled to recycle through line 95 to recycle fatty acid tank 19.
The lower phase in secondary phase settler 83 is an alcohol-brine (or alcohol-water) phase which is recycled through line 87 by pump 85 to the alcohol-water tank 31. It will be seen from the foregoing description that the method and apparatus shown in FIGURE 1 provides a recycling of solvents and particularly the fatty acid solvent in a manner which is reLatively simple compared to processes involving saponification or other previous processes and is at the same time much less energy intensive than distillation techni-ques for the separation of fatty acid solvent from the hydrocarbon product. For an illustrative flow rate table, see Table 1.
The method and apparatus of FIGURE 2 is generally similar to that of FIGURE 1, and differs primarily in the technique for separating and recycling the fatty acid and the alcohol-water components.
I-t should be understood that all reference to fatty acid in the drawings and in -the description identifies the preferred forms of carboxylic acids for most purposes as presently contemplated.
In general these references to fatty acid could be replaced by "carboxylic acids havin~ from 8 to 20 carbon atoms or admixtures thereof".
Light hydrocarbons to be employed as an auxiliary diluent may include, 3'7~
but are not limited to, alkanes such as propane, butane, pentane, hexane, and heptane.
In FIGURE 2, lines 113 and 115 supply fatty acid and light hydrocarbon solvents to the system while recycled fatty acid is supplied from tank 119 all through line 117 to solvation contactor 123. The bitumen source material is supplied through channel 111 and the outputs from solvation contactor 123 are solvated bitumen through line 127 and sand or other waste material through channel 125.
A mixture o~ solvated bitumen with alcohol-water (or alcohol-brine) is supplied Erom tanks 129, 131 and 135 through lines 137, 141 and 145 respec-tively to input line 149 for blender 151. The liquids are transported under the control of pumps 139, 143 and 147, all as generally described with regard to FlGURE 1.
Blender 151 feeds the primary settler 155 through line 153 and an optional heater 157 is provided for the primary settler 155 as previously described. Bitumen-derived product is extracted from the lower phase of settler 155 and fed to product storage 161. Of course further processing of the bitumen-derived product may be carried out with conventional techniques to produce certain desired useful hydrocarbon end products.
An acid-alcohol-water stream is extracted from settler 155 through line 163 and may be transported by a pump 165; The process and apparatus of FIGURE 2 employs a technique in the second settling step which takes advantage of further phase separation of the fatty acid from the alcohol-water to remove and recycle the fatty acid (or other carboxylic acid) utilized in the process. For this technique additional process water is added through a throttle valve 17~ in line 168 to be combined in blender 178 and fed through line 177 to secondary settler 183. I-t might be noted that Ln theory the func-tion of primary settler 155 and settler 183 might be combined in a process of phase separation into three phases consisting of, from top to bottom;
337~
carboxylic acid, alcohol-water (or alcohol-brine), and bitumen-derived product. Thus while it would be within the scope of the invention to separate these three distinct phases in one settler apparatus, the practical difficul-ties thereof make the process utilizing tWQ separa-te steps of gravity separation preferable in the usual circumstances contemplated .
Pump 181 in input line 177 and pumps 185 and 191 in output lines 187 and 189 from settler 183 perform a usual function of transporting the liquid process chemicals. As explained before, the number, position and character of the pumps utilized is not limited to that shown, but will be determined by conventional process appara-tus design techniques for a designated process and apparatus.
As will be seen from the apparatus thus far described, inline mixer or blender 178 together with process water input through line 168 in FlGURE 2 replaces boiler 67, condenser 71, and fin-fan cooler 79; thus in FIGURE 2 process water is mixed in line 177 before being pumped to secondary settler 183. This achieves the same result as the boiler and condenser, because both processes increase the water content of the stream to the secondary settler to cause shifting in the phase equilibrium in the secondary settler 183. Thus phase sepa-ration is effectively produced in set-tler 183 allowing the fatty acid or carbo~cylic acid to be drawn off the top phase and recycled.
If water overdosing is used as shown in FIGURE 2, then a distillation column 192 is used to recover alcohol in greater concentra-tion from the stream in line 187. A dilute brine waste stream is pumped to disposal through line 194 by means of pump 196 while suitable concentrated alcohol-water is recovered overhead in line 173 after condensation in condenser 171.
The distillation process effected by column 192 is a relatively low energy requirement process particularly if suitable heat recovery techniques are employed. By way of example waste heat may be 3~
employed for heater 157 which requires a temperature of only about 50 degrees Celsius.
From -the above description of FIGURE 2 it will be seen that an alternative separation process for the fatty acid relative to the alcohol water component is provided which may in many cases be more cost effective than that of FIGURE 1. In particular it will be seen that the FIGURE 2 apparatus and method does not require that the fatty acid component be heated and subsequently cooled as a part of the processing of the recirculating stream of carboxylic acid solvent.
FIGURE 3 shows a flow diagram of a modification of the process of FIGURE 2 which differs primarily in that a series of reverse osmosis units 225 of conventional design are employed to reconcentrate a brine solution for return to initial blender 213.
The added complexity of the process of FIGURE 3 achieves a more complete recovery of process chemicals and endeavors to eliminate any chemical waste products or limit them to water or other environ-mentally innocuous materials. The basic process of FIGURE 3 is essentially similar to that shown in FIGURE 1 or more specifically that shown in FIGU~E 2. Namely a carboxylic acid solvated bitumen solution 211 is fed to a blender 213 which is also supplied with an alcohol-brine solution whereupon the composite admixture is transported into a primary settler 215 so that amphiphilic phase separation will permit gravity separation of product bitumen from the lower phase while the brine, alcohol and acid process chemicals are fed to blender 217 which is also supplied with overdosing water from reverse units 225 thereby generating a suitable solution for settling in secondary se-ttler 218.
An upper phase of carboxylic acid is removed from secondary settler 218 while brine and alcohol is supplied to a brine tower 240 including cooler 244 for extracting an ( isopropyl~ alcohol s-tream.
In order to balance the flow rates in the process illustrated in E;IGURE 3 (to minimize or eliminate disc:harge streams) the alcohol-water stream from brine tower 240 receives further alcohol concentration in I~A tower 247. This brings the alcohol concentration in the recycled alcohol-water stream above the azeotrope concentration of approximately 70 percent by weight alcohol. Tank 251 aids in controlling flow rates, and water therefrom is added to the stream supplying the distillation column of brine tower 2G,0. ~ Understanding of FIGURE 3 will be aided by reference to Table 11 which gives exemplary flow rates for a system such as illustrated in FIGURE 3.
From the foregoing explanation it will be seen how selected process steps in conventional or known chemical process apparatus are combined according to the invention for recovering oil or bitumen-derived products in a method which is characterized by the efficient recovery of carboxylic acid and other process chemicals employed in the amphiphilic phase separation procedure.
The following examples of processes according to the invention with specific materials, flow rates, times, temperatures and other parameters should be considered to be illustrative and not restrictive of the scope of the present invention. All proportions stated in the examples are by weight unless otherwise indicated.
A solvated bitumen solution containing approximately 20 percent by weight of Kentucky bitumen, 8 percent isopropyl alcohol, 24 percent ligh-t hydrocarbon solvent such as heptane, and 48 percent tall oil derived t`atty acid solvent, such as Xtol 304, is fed to a blender 51 at a ra te of 4 .1 gpm . An alcohol/brine solution containing 68 percent isopropyl alcohol (2-propanol) and 32 percent 2500 ppm brine solution is simultaneously fed to this blender at a rate of 12.9 gpm. Under these feed conditions the product stream in line 59 from settler 55 ~ Z~ 37'~
produces 5~0 Ib/hr of a bitumen rich product containing 54 percent bitumen, 6 percent isopropyl alcohol, 38 percent heptane, and 2 percent fatty acid. The fatty acid rich solvent recycle stream would produce 1070 Ib/hr through line 89 containing 77 percent fatty acid, 7 percent bitumen, and 16 percent heptane. The concentration oE
alcohol in the alcohol/brine stream as well as the ratio of stream in line 37 to stream in lines 41 and 45 may be varied in order to procduce a variation in bitumen product stream 59. The residence times in pri mary settler 55 and in secondary settler 83 are resepctively less than 30 minutes and preferably, approximately 10 minutes.
See Table 1 below.
The procedures are the same as in Example 1, except an admixture of one or more vegetable-derived fatty acids such as soybean oil, cottonseed oil, safflower oil, palm oil, or corn oil, is used in place of all or part of the tall oil derived fatty acid. This prevents the hardening of the bitumen product that may occur in some cases because of small amounts of resin present in the tall oil derived fatty acids.
The procedures are the same as Example 1, except that the alcohol/brine stream through line 49 from tanks 31 and 35 is composed of approximately 85 percent by weight methanol and 15 percent by weight of pure water. The result is a much more fluid bitumen product containing high concentrations of fatty acid. This mode of operation is useful to provide an asphaltic blending stock for roacl pavlng. The fatty acid serves as an emulsifier in the paving asphalt .
33~
EXAl~IPLE 4 The procedures are the same as Example 1, except the alcohol/
brine stream is an admixture of at least 10 percent of two different forms of alcohol containing methanol, ethanol, l-propanol, 2-propanol, and/or butanol, to meet specified bitumen-derived product composition and characteristics. The exact admixture composition varies depending upon differences in chemical composition of the feedstock bitumen and the amount of bitumen in the feedstock stream.
E~ PLE
The procedures are the same as in a selected one of Examples, 1 to 4, except at least the bottom phase in primary settler 55 is heated to 40-50 C. resulting in a purer bitumen product in some instances .
The procedures are the same as Example 5, except the bottom phase in primary settler 108 is heated to 90-110 C. or greater to achieve a granular, solid bitumen product upon cooling. This product may be suitable for production of carbon black.
The procedures are the same as Example 1, except the brine concentration in the alcohol/brine stream is varied from 0 percent to 10 percent depending upon the bitumen feedstock properties to achieve a bitumen product containing a predetermined desired amount of fatty acid to serve as an emulsifier or for other purposes. lt is also possible in some cases to achieve desired product characteris-tics by varying the ratio of the alcohol/brine stream to the solvated bttumen stream between the ratios of 1:1 to 5:1.
337~
E~AMPLE
The procedures are the same as a selected one of Examples 1 to 7 except the residence time in primary settler 108 and secondary settler 109 is varied between 1 and 10 minutes in order to vary the composi~ion of the product bitumen stream.
EXA~PLE 9 The procedures are the same as a selected one of Examples to 8 ex cept the procedure of water overdosing as shown in FIGURE 2 is used to achieve phase equilibrium shift in secondary settler 183, and subsequent distillation is used to recover the alcohol. A dilute brine stream is discharged to salt water disposal.
The procedures are the same as Example 9 except reverse osmosis and a two distillation column system are used to recover both the alcohol and the brine, thereby substantially eliminating all discharge streams. FIGl~RE 3 shows the process flow diagram for this example, and Table 2 presents the process stream mass balance for a 336 barrel/day demonstration plant. For illustrative purposes, the product bitumen stream, line 5, was assumed to be pure bitumen in the calculations shown in Table 2.
The procedures are the same as Examples 1, 3, 4 or 5-8 except the Xtol 304 solvent is replaced by commercial oleic acid.
EXI~MPLE 12 The procedures are the same as Examples 1, 3, 4 or 5-8 except the X-tol 304 solvent is replaced by dithiobenzoic acid.
'~ Ir~
A solvated bitumen solution containing approximately 10-20 percent Fitzgerald (Oklahoma) tar sand, 5-10 percent isopropyl alcoholt 20-25 percent light hydrocarbon solvent such as heptane, and 40-60 percent acid solvent formed of an admixture of one or more of the vegetable-derived fatty acids consisting of soybean oil, cottonseed oil, safflower oil, palm oil, and corn oil, is fed to in-line blender ~1 or lSl at a rate of 4-5 gpm. An alcohol/brine solution containing 60-80 percent isopropyl alcohol (2-propanol) and 1000-3000 ppm brine solution is simultaneously fed to this blender at a rate of 10-15 gpm. The concentration of alcohol in the alcohol/
brine stream as well as the ratio of such stream to the feedstock stream may be varied in order to produce a variation in bitumen product. The residence times in primary settler 108 and in secondary settler 112 are respectively approximately 5 to 15 minutes.
EXA~IPLE 14 The procedures are the same as Example 13, except the alcohol/
brine stream is an admixture of 2 or more alcohols containing methanol, ethanol, I-propanol, 2-propanol, and/or butanol, to meet specified product composition and characteristics. The exact admixture composition is varied depending upon differences in chemical composition of the feedstock bitumen and the amount of bitumen in the feedstock.
I'he procedures are the same as in a selected one of Examples 12-14, except the bottom phase in primary settler 55 is heated to 40-50 C.
EXAI~lP~E 16 The procedures are the same as Example 13, except the brine concentration in the alcohol/brine stream is varied from 0 percent to 10 percent depending upon the bitumen feedstock properties to achieve a bitumen product containing varying amounts of fatty acid as may be desirable in some cases.
EXAl~PLE 17 ~ solvated bitumen solution containing approximately 20 percent by weight of Kentucky bitumen, 8 percent isopropyl alcohol, 24 percent light hydrocarbon solvent such as heptane, and 48 percent carboxylic acid solvent, such as dithiobenzoic acid, is fed to a blender at a rate of 4.1 gpm. An alcohol/brine solution containing 68 percent isopropyl alcohol (2-propanol) and 32 percent 2500 ppm brine solution is simultaneously fed this blender at a rate of 12.9 gpm. The concentration of alcohol in the alcohol/brine stream as well as the ratio of stream in line 37 to stream in lines 41 and 45 may be varied in order to produce a variation in bitumen product stream 59. The residence times in primary settler 55 and in secondary settler 83 are respectively less than 30 minutes and preferably, approximately 10 minutes.
The above exa~ples are illustra-tive only, and those skilled in the art will appreciate that there are numerous variations which can be employed in virtually innumerable combinations. While tar sands have been specified as bitumen source material because of their potential economic importance, other bitumen source ma-terials could be substituted, with adjustment of process parameters in some cases .
Various fatty acids have been enumerated in -the examples, but there is a wider range of carboxylic acids ( generally those having 8 to 20 carbon atoms) among which selection may be made ~.x~3t7~
based on contemporaneous price and availability or other factors.
Potential carboxylic acids for use in the process include but are not limited to the following: -mono and/or poly alkanoic acid, alkenediolic acid, alkenoic acid, alpha linoleic acid, aracadonic acid, arachidic acid, benzilic acid, bethinic acid, dithiobenzoic acid, gamma linoleic acid, hydroxyalkanoic acid, lauric acid, lignoceric acid, linoleic acid, linolenic acid, myristic acid, naphthenic acid, octadecenoic acid, oleic acid, palmitic acid, petroselaidic acid, stearic acid, tetranoic acid, thiocarboxylic acid, and/or truenoic acid.
In the same vein, alcohols for use in the process may be selected as much on the basis of current cost and availability as on other factors. Similarly, brine when referred to above is contem-plated to be a solution of water and predominantly sodium chloride, but the process is not limited to sodium chloride as the brine component, and in fact, the brine component may be omitted in some cases.
While the above described theory of operation of the process is thought to be responsible for the observed efficient separation and recovery of carboxylic acids and other advantages of the invention, the novelty and advantages of the process are not attributable to the theory presented but are due to actual results established by experimentation. Accordingly, patentability of the invention is not to be considered to be dependent on the theory presented above, although any theory presented, so far as it is known, is believed to be correct. The steps recited in the claims may in some cases be performed in a different sequence than the sequence in which they are listed, or steps may be performed concurrently.
In addition to the variations and modifications to the invention which have been described or suggested, numerous other variations or rnodifications will be apparent to those skilled in the art.
Accordingly the scope of the invention is not to be considered to 7~
be limited to the embodiments and variations described but is to be determined by re:ference to the appended claims.
~ %~3~37~:
O ~ O ~ 00U~ ~ ~ ~D
,, o ~ ~ ~ oo o o ~ ~ U~
O 1~ u; ~ O O
o u~
E~ i~ u~ ~ 0`J
. ,~ u~
.
_~o a~ o o~ oo~ O
o ~ ~ ~ o o ~ o ~ o . ~ ~ o o o o o o ~ U'~ o U~ o O ~ ~ ~ O ~ ~ o r~ o r~ r~ OD CO 0 ~a u~ ~ u~ ~ O O
_, ~ ~ ~ ,.
o o o U~ ~~ ~ o o o o ~ i o " U~
~ o U'~ ~ ~ o~ o o o o .~ ~ ,_ ~ ~ ~ ~~ ~r o~ c~
~ ~1 ~D 0 r~ r~ o ~ a:
.
~,-8 o 8 8 8 o o . o o R 9 o o o u~ u~o ~ u~ o o P~ ~ ~ U~ U~ ~ ~ ~ ~
,~ ~ ~ ~ ~ , ;
Cl ~ I~ co ooo ~ o O 00 ~ ~i ~D O ~ ~ CO O
~; C`03 ~; ~; o oo C~O~
~o o o ~ ~ ~ ~ U~ U~ o o O ~ `D O ~D ~D ~ ~ O O '.~' U~ ~ ~ ~ , oo ~;~ ~ U~ ~ ,, ,, ~ C`~
I~ ~ a~ ~ ~ O ~ ~ 0 u~
0 ~ O O O 1` ~ 0 ~3 0 U~ ~o ~ t- o ,1 ~ ,, ~ ~ ~ ~ `D 8 `D ~ ~ `D
~1 U~ U~
~ ~ o o o o o o o o o r~ r ~ ~) O~ 1~) 1~ C~ I~ ~n ~i ~ n ~ ~n r~ ~ ~ ~ ~
~ ~ D ~ ~ ~
h v~ tn u~
.
~ ~83 1~ f~C 69370--7 N l l O l l l l O
N I I O l ~ ~-1 N ~ N
N l l N ~ I ~; 01 ~
N l l N I I _ N ~p N I I$ I I ~9 ~
N I I~ I N ~D
N _ P N
N ~ ~O ~D
N _~ N
N _ _ ~ ~ I 1~ ~
1~ ~ ~N l ll I ~ l d' ~ N 1-1 . U-N ~r ~
1_~ g~ N ~O ~'I
a~ , ~ I o I u7 8 ~ , u~ I I
_ O N ~ I N ¦ ;~
O N _~
O I I l_CO I I I _ ~ l ~ r~
N ~ , ~!;
_ ~
O ~ ~ 00 1 1 1 ~
, 1
AMPHIPHILIC PHASE BE~AVIOR SEPARATION
OF CARBOXYLIC ACIDS/HYDROCARBON MIXTURES IN RECOVERY
OE' OIL FROM TAR SANDS OR THE LIKE
The present invention rela-tes primarily to heavy oil and bitumen recovery systems using carboxylic acids, (and in most cases also l;ght hydrocarbons) as extraction solvents for recovering the oil or bitumen components and is particularly characterized by the efficient recovery of the carboxylic acid components for recycle purposes. The molecules of selected acids used will normally contain from 8 to 20 carbon atoms.
This recovery is accomplished by a low-energy, alcohol-induced amphiphilic phase separation procedure. It also may find application in fractionating light hydrocarbon components from heavy hydrocarbon components in the oil or bitumen. For rea-sons of economy, carboxylic acids within the group known as fatty acids will genera]ly be employed; fatty acids is a -term given to monobasic aliphatic carbo~ylic acids.
There are two basic approaches to recovering heavy oil or bitumen. The tar sand resource may be mined and trans-ported to a process plant where the bitumen is extracted using solvents, or the separation may be accomplished in situ. In situ processes have a great deal in common with secondary or enhanced recovery of conventional lighter crude oil.
Conventional ligh-t crude oil is produced from the oil-bearing formations by drilling wells down into the forma-tion. The oil usually is driven from the ~ormation into the wells (production wells) by energy stored in the formation, such as the pressure of natural gas. When this natural energy of the Eormation is expended or, as in the case of most tar sands if it never was present, then energy must be injec-ted into the formation (via injection wells) in order to stimulate production. A third essential element for a successful in situ process is a means of communication between the injection ~, 7 3.2~33'^~
wells and the production wells.
In the case of heavy oil tar sand in situ production, solvating chemical agents and/or steam are often used as the injection fluid in -the injection wells. ~Iydraulic fracturing techniques are usually used to generate communication between injection and production wells. The solvating agent normally would be an admixture of ei-ther a light hydrocarbon diluent, an emulsifying agent with water, or in the case of the present invention a carboxylic acid admixture which may also include a light hydrocarbon.
The alternative to an in situ processing scheme is to mine the tar sands, transport them from their place in the formation to a processing plant, extract the bitumen value, and dispose of the waste sand. The emphasis in the following description is on the mined tar sands approach, but in situ processing is not excluded.
Shaft mining of tar sands is considered impractical because of economic considerations, but could theoretically be employed. There are two approaches to the open pit mining of tar sands. The first is to use a few mining units of custom design, which will necessarily be very expensive. E;or instance, large units which have been considered are bucket wheel excavators, dredges ( both hydraulic and bucket ladder) and super-sized draglines. The other approach is to use a multiplici-ty of smaller mining units of conventional design and relatively much lower unit costs. For example, scrapers and truck-and-shovel operations may be considered. Each method has advantages for par-ticular situations.
The solvent extraction processes used in conjunction with surface-minecl tar sand opera-tions vary primarily with respect to contacting-device used to extract the solvated bitumen from the sand particles and with respect to the means of recovery of the solvating agent for recycle purposes. The traditional method for separation of solverlt 8~3~
from crude oil is distillation which is energy intensive and often renders a process economically and ecologically unattractive. Losses of solvent associated with the spent sand may also decrease the economic feasibility of the process. The present invention contemplates the use of amphiphilic phase behavior to bring about a low energy requirement for recovery of the solvent and may utilize a wa-ter enhanced washing scheme in order to minimize solvent losses to the spen t s and .
In U. S. Patent No. 4,480,691 entitled "Recycle~ Fat-ty Acid Crude Petroleum Recovery Process" issued to ~lerter et al. on November 6, 1984, there is described a method of recovering crude oil from materials such as tar sands, kerogen or the like wherein the crude oil source is treated with a fatty acid to produce a solvated crude oil mixture of reduced viscosity. The fatty acid in this mixture is then saponified by re~cting it with an aqueous base such as an alkali metal hydroxide to separate the solvated mixture into petroleum crude and an acid soap which will Inigrate into the aqueous phase.
The petroleum crude is separated from the aqueous soap solution and subsequently the fatty acid is recovered by a desaponification s-tep which is conducted in the presence of an acid. Car~onic acid can be generated for the desaponifying step by injecting high pressure carbon dioxide with the desaponification treating vessel. Additional refining can take place by other separation or filtration steps.
In that Herter process, the efficiency of recovery of the fatty acid solvent for further use represents a prime economic consideration.
~lowever, it has been found that as a result of emulsification in the saponification portion of the process, the economic practicality of solvent recovery used in the Herter process is limited. There has been some progress to improve the Herter process by reducing or eliminating emulsification in the saponification step.
3837~
Although -there have been numerous prior applica-tion of carboxylic acids and especially fatty acids in enhanced oil recovery, these applications use the fatty acid salts or soaps and their derivatives as surfactants, while the Herter process and related processes use a free carboxylic acid as a solvating chemical agent.
An economically important portion of the Herter process and tar sand processes generally concerns the recovery of fatty acid or other solvent from the solvated hydrocarbon mixture.
Fatty acids tend to form azeotropes with most desired petroleum fractions, making the refining of crude oil containing fatty acids much more difficult. Separation of fatty acids from such a mixture by a method other than distillation is thus highly desirable. The approach used in Herter and related processes is saponification oE
the solvated mixture with an aqueous base, followed by migration of the resulting soap into the aqueous phase, and then desaponification of the aqueous phase to regenerate the fatty acid.
The present invention is an improvement (over the Herter and related processes) utilizing amphiphilic phase behavior for carboxylic acid recovery and thereby eliminating the need for both the saponifi-cation and desaponification steps of the Herter process. The present invention may be applicable to separations of carboxylic acids and hydrocarbon mixtures in t'ne fractionations of heavy oil or bitumen into asphaltene and malthene components. When the bitumen or oil feed material is other than tar sand, the invention may be used in cleaning up oil spills, reducing the viscosity of heavy oil or bitumen for transportation by pipeline, the reclaiming of used oil, and the recovery of sur~actants from oil admixtures.
Prior patents in other technologies such as Donald V. Julian, "~ec~ es Patent No. 3,691,211, Sept. 2, 1972, -to Procter & Gamble Co. have suggested phase separation to recover acid process material for 3 7;?d recycling, but the actual process employed has no applicability to crude oil recovery processes as provided by the present invention.
The present invention makes use of carboxylic acids (with 8 to 20 carbon atoms) or carboxylic acid mixtures as a solvent or diluent which is mixed wi-th an oil, injected into an oil reservoir, or mixed with tar sands in a surface vessel -to reduce the viscosity of the crude oil and to increase the mobility of the oil. This feature is also found in the Herter process. However, the present invention differs in its unique process for recovery of carboxylic acid diluent by amphiphilic phase separation induced by alcohol injection whereas Herter et al proposed the separation of fatty acid from a petroleum mixture by saponification of the solvated mixture with an aqueous base, followed by migration of the resulting soap into the aqueous phase, and then desaponification of the aqueous phase to regenerate the fatty acid. Specifically, the present invention contemplates using a lower alcohol containing from l to 8 carbon atoms as an amphiphilic cosolvent with the carboxylic acids and preferably employs isopropanol or n-butanol for this purpose. An aqueous brine solution may also be used to enhance the amphiphilic phase separations. Acids used in accordance with the present inven-tion are usually straight chain carboxylic acids containing between 8 and 18 carbon atoms. The invention may alternatively make use of naturally occurring saturated carboxylic acids with carbon chain lengths between 12 and 20, as well as unsaturated carboxylic acids with a carbon chain length of up to 20 a-toms. These unsaturated acids have lower melting points than the corresponding saturated acids and remain liquids at lower temperatures than the saturated fatty acids, making them attractive for use in the process. Three common unsaturated fatty acids which can be used in connection with the presen-t invention are oleic acid, linoleic acid, and linolenic acid. ~iixtures of fatty acids or acids containing irnpurities such as rosin acids can also be employed.
. ~
~ 2~3~3~7~
It is contempla-ted that a combination of the present invention and a Herter acid regeneration process arranged in series could prove advantageous. The present invention would bring about a rough cut of the separation of carboxylic acids from the many hydrocarbons and the Herter process would accomplish a higher purity separation when this i5 desired.
After the carboxylic acid components are separated from the bitumen-derived components according to the present p.rocess there is still a need to individually separate the acid components and the alcohol-water components for recycling pur-poses.
The alcohol-water and acid components may be separa-ted in a straightforward manner by distillation techniques.
Such conventional techniques are suitable for this separation process because, unlike the separation of the carboxylic acid and bitumen product, separation of the alcohol and water from the carboxylic acids is not difficult or especially energy ,.
in-tensive; thus with conventional energy conservation proce-dures such distillation can be cost effective.
According to the invention a different separation procedure may be employed to achieve better economy in some cases. This involves mixing process water with the carboxylic acid and alcohol admixture to achieve water overdosing which shifts the phase equilibrium and allows gravity separation of the carboxylic acids component. Following this step, only very simple and efficient distillation methods may be used to separate the alcohol from its water or brine diluent. Alcohol does not need to be obtained in a pure form Erom this process and may contain significant amounts of water because the pro-cess input normal alcohol-water composition is below the 6g370-7 azeotrope composition. This significantly reduces the energy requirements of the ~alcohol concentrating step.
In addition to providing the above described features and advantages it is an object oE the present invention to provide a ~ 6a -~r ~: ` .".
34~
process for separation of carboxylic acid admixtures from hydrocarbons useful in processes such as the recovery of oil from tar sands or the like wherein an adrnixture of carboxylic acid usually also containing light hydrocarbons such as heptane is combined with a bitumen source as an extraction solvent after which amphiphilic phase behavior separa-tion of the carboxylic acid component is achieved by introducing an alcohol-water or alcohol brine solution into the mixture.
I t is another ob ject of the present invention to carry out the above process utilizing carboxylic acids having 8 to 20 carbon atoms and to gravity separate the carboxylic acid and alcohol-water component for recovery of the acid and alcohol components for recycling use .
It is still another object of the present invention to provide a process as described above wherein separation of the carboxylic acids is achieved in part by water overdosing the admixture resulting from the process and thereafter gravity separating the carboxylic acid from the alcohol-water component.
Other objects and advantages of the invention ~ill be apparent from consideration of the following description in conjunction with the appended drawings in which;
FIGURE 1 is a schematic diagram showing apparatus and process employed to carry out the methods according to the present invention;
FIGURE 2 is a schematic diagram showing an alterna-tive apparatus and process including water overdose phase separation for recovery of recycle acid from the acid-alcohol-water process stream; and FIGURE 3 is a schematic flow chart diagram of a process according to the invention showing more extensive recycling of process chemicals for environmental prolection.
Referring now to the drawings, FIGURE 1 shows a basic preferred process and apparatus therefor according to the invention. Bitumen source material is input through a channel 11 suitable for the solid or semi-solid tar sands or other bitumen source material. Solvent input 17 is connected to lines 13 and 15 for input of fatty acid and light hydrocarbon solvents. A holding tank 19 for recycled fatty acid also feeds the solvent input 17. Line 21 supplies recycled fatty acid to holding tank 19 from a source later to be described.
A solvation contactor 23 of known construction is provided to receive bitumen source material through channel 11 and solvent liquids through line 17. Solvation contactor apparatus of suitable form is shown in U.S. Pat. 4,311,561 dated Jan. 19, 1982, to Larry W. Hastings entitled "Apparatus for Extracting Bitumen from Tar Sand."
Other apparatus for contacting tar sand or other bitumen source with solvent to efficiently produce solvated bitumen is referred to in the above patent. Solid waste from the solvation contactor 23 exits through channel 25. In some cases the sand from solvation contactor 23 may be washed or otherwise processed and usefully employed in the production of glass or as a raw material in some other manufacturing process. Treatment of the waste from the solvation contactor 25 does not, however, form a part of the present invention.
Solvated bitumen is transferred through line 27 to a holding tank 2~. Alcohol-water mixture utilized in the process is stored in holding ~ank 31. Tank 31 is supplied through line 33 from recycling apparatus to be later described. At least a small quantity of alcohol ( typically isopropyl alcohol) will be lost in the process and must be made up. Tank 35 contains the make up alcohol.
A blender 51 has a supply line 49 which is connnected to receive solva ted bitumen through line 37, alcohol-water through line 41 and makeup alcohol through line 45; pumps 39, 43 and variable delivery pump 47 serve to produce and control the flow of liquids to blender 51.
It will be understood that while pumps are shown in particular locations in the diagram of FIGURE 1, it is basically a schematic diagram and actual pump locations and flow line connections would 8~
be determined in accordance with conventional techniques of chemical plant design. The same is true of FIGURE 2. Neither the number or the location o-E the pumps illustrated is critical to the design of the appar~tus for carrying out the process of the invention.
While tank 31 is designated an alcohol-water tank, in many cases the process will be more effective with brine rather than water being admi~ed with the alcohol. In other words the water of tank 31 may have and usually will have sodium chloride or a similar salt in solution.
The alcohol content of the alcohol-brine solution fed to blender 51 with the solvated bitumen may be varied by opera-tion of the variable delivery pump 47. Other means of a con-ventional type may be employed to control the materials propor-tions for blender 51. Blender 51 is conven-tional liquid blend-ing apparatus employing mechanical agitation or other suitable mechanism for attaining a homogeneous mixture. A primary phase settler 55 is fed directly from blender 51 ~hrough line 53. In settler 55 a phase formation takes place resulting in gravity separation of a lower heavy hydrocarbon phase containing small or insignificant amounts of alcohol, brine, and acid process chemicals. Other means for separating liquids of different density could be used in place of conventional set-tler 55. The heavy hydrocarbon phase is removed through line 59 and pumped or otherwise transported to product storage tank 61.
The eeficiency of the process may be i.mproved if the lower phase in settler tanlc 55 is heated to Erom ~0 C. to 50 C. or higher temperatures and an optional heater 57 may be employed for that purpose. The upper phase (or phases) of primary settler 55 contains virtually all process constituen-ts 1"
~ 3~ 69370-7 except for the bitumen-derived hydrocarbon product and light hydrocarbon diluent, and the remaining upper phase constituents are fed through line 63 by means of pump 65 to a boi:ler 67.
Boiler 67 feeds a condenser 71 through line 69 ~ 9a -. ",,~ .
~ ~13t'33~.
whereby an alcohol-rich vapor phase is condensed and transported through line ~i3 by pump 75 to alcohol-water tank 31. In some cases it may be necessary or desirable to replace boiler 67 and condenser 71 with a distillation column of two or more stages for higher concen-tration of alcohol in line 73.
The liquid phase from boiler 67 is passed into line 77; after being cooled by fan cooler 79 it is delivered by pump 81 to secondary phase settler 83.
After reduction of the alcohol concentration in line 77 phase separation takes place in secondary settler 83 wherein the upper phase is the fatty acid constituent which is delivered through line 89 by pump 91 to fatty acid hold tank 93, where it may be controlled to recycle through line 95 to recycle fatty acid tank 19.
The lower phase in secondary phase settler 83 is an alcohol-brine (or alcohol-water) phase which is recycled through line 87 by pump 85 to the alcohol-water tank 31. It will be seen from the foregoing description that the method and apparatus shown in FIGURE 1 provides a recycling of solvents and particularly the fatty acid solvent in a manner which is reLatively simple compared to processes involving saponification or other previous processes and is at the same time much less energy intensive than distillation techni-ques for the separation of fatty acid solvent from the hydrocarbon product. For an illustrative flow rate table, see Table 1.
The method and apparatus of FIGURE 2 is generally similar to that of FIGURE 1, and differs primarily in the technique for separating and recycling the fatty acid and the alcohol-water components.
I-t should be understood that all reference to fatty acid in the drawings and in -the description identifies the preferred forms of carboxylic acids for most purposes as presently contemplated.
In general these references to fatty acid could be replaced by "carboxylic acids havin~ from 8 to 20 carbon atoms or admixtures thereof".
Light hydrocarbons to be employed as an auxiliary diluent may include, 3'7~
but are not limited to, alkanes such as propane, butane, pentane, hexane, and heptane.
In FIGURE 2, lines 113 and 115 supply fatty acid and light hydrocarbon solvents to the system while recycled fatty acid is supplied from tank 119 all through line 117 to solvation contactor 123. The bitumen source material is supplied through channel 111 and the outputs from solvation contactor 123 are solvated bitumen through line 127 and sand or other waste material through channel 125.
A mixture o~ solvated bitumen with alcohol-water (or alcohol-brine) is supplied Erom tanks 129, 131 and 135 through lines 137, 141 and 145 respec-tively to input line 149 for blender 151. The liquids are transported under the control of pumps 139, 143 and 147, all as generally described with regard to FlGURE 1.
Blender 151 feeds the primary settler 155 through line 153 and an optional heater 157 is provided for the primary settler 155 as previously described. Bitumen-derived product is extracted from the lower phase of settler 155 and fed to product storage 161. Of course further processing of the bitumen-derived product may be carried out with conventional techniques to produce certain desired useful hydrocarbon end products.
An acid-alcohol-water stream is extracted from settler 155 through line 163 and may be transported by a pump 165; The process and apparatus of FIGURE 2 employs a technique in the second settling step which takes advantage of further phase separation of the fatty acid from the alcohol-water to remove and recycle the fatty acid (or other carboxylic acid) utilized in the process. For this technique additional process water is added through a throttle valve 17~ in line 168 to be combined in blender 178 and fed through line 177 to secondary settler 183. I-t might be noted that Ln theory the func-tion of primary settler 155 and settler 183 might be combined in a process of phase separation into three phases consisting of, from top to bottom;
337~
carboxylic acid, alcohol-water (or alcohol-brine), and bitumen-derived product. Thus while it would be within the scope of the invention to separate these three distinct phases in one settler apparatus, the practical difficul-ties thereof make the process utilizing tWQ separa-te steps of gravity separation preferable in the usual circumstances contemplated .
Pump 181 in input line 177 and pumps 185 and 191 in output lines 187 and 189 from settler 183 perform a usual function of transporting the liquid process chemicals. As explained before, the number, position and character of the pumps utilized is not limited to that shown, but will be determined by conventional process appara-tus design techniques for a designated process and apparatus.
As will be seen from the apparatus thus far described, inline mixer or blender 178 together with process water input through line 168 in FlGURE 2 replaces boiler 67, condenser 71, and fin-fan cooler 79; thus in FIGURE 2 process water is mixed in line 177 before being pumped to secondary settler 183. This achieves the same result as the boiler and condenser, because both processes increase the water content of the stream to the secondary settler to cause shifting in the phase equilibrium in the secondary settler 183. Thus phase sepa-ration is effectively produced in set-tler 183 allowing the fatty acid or carbo~cylic acid to be drawn off the top phase and recycled.
If water overdosing is used as shown in FIGURE 2, then a distillation column 192 is used to recover alcohol in greater concentra-tion from the stream in line 187. A dilute brine waste stream is pumped to disposal through line 194 by means of pump 196 while suitable concentrated alcohol-water is recovered overhead in line 173 after condensation in condenser 171.
The distillation process effected by column 192 is a relatively low energy requirement process particularly if suitable heat recovery techniques are employed. By way of example waste heat may be 3~
employed for heater 157 which requires a temperature of only about 50 degrees Celsius.
From -the above description of FIGURE 2 it will be seen that an alternative separation process for the fatty acid relative to the alcohol water component is provided which may in many cases be more cost effective than that of FIGURE 1. In particular it will be seen that the FIGURE 2 apparatus and method does not require that the fatty acid component be heated and subsequently cooled as a part of the processing of the recirculating stream of carboxylic acid solvent.
FIGURE 3 shows a flow diagram of a modification of the process of FIGURE 2 which differs primarily in that a series of reverse osmosis units 225 of conventional design are employed to reconcentrate a brine solution for return to initial blender 213.
The added complexity of the process of FIGURE 3 achieves a more complete recovery of process chemicals and endeavors to eliminate any chemical waste products or limit them to water or other environ-mentally innocuous materials. The basic process of FIGURE 3 is essentially similar to that shown in FIGURE 1 or more specifically that shown in FIGU~E 2. Namely a carboxylic acid solvated bitumen solution 211 is fed to a blender 213 which is also supplied with an alcohol-brine solution whereupon the composite admixture is transported into a primary settler 215 so that amphiphilic phase separation will permit gravity separation of product bitumen from the lower phase while the brine, alcohol and acid process chemicals are fed to blender 217 which is also supplied with overdosing water from reverse units 225 thereby generating a suitable solution for settling in secondary se-ttler 218.
An upper phase of carboxylic acid is removed from secondary settler 218 while brine and alcohol is supplied to a brine tower 240 including cooler 244 for extracting an ( isopropyl~ alcohol s-tream.
In order to balance the flow rates in the process illustrated in E;IGURE 3 (to minimize or eliminate disc:harge streams) the alcohol-water stream from brine tower 240 receives further alcohol concentration in I~A tower 247. This brings the alcohol concentration in the recycled alcohol-water stream above the azeotrope concentration of approximately 70 percent by weight alcohol. Tank 251 aids in controlling flow rates, and water therefrom is added to the stream supplying the distillation column of brine tower 2G,0. ~ Understanding of FIGURE 3 will be aided by reference to Table 11 which gives exemplary flow rates for a system such as illustrated in FIGURE 3.
From the foregoing explanation it will be seen how selected process steps in conventional or known chemical process apparatus are combined according to the invention for recovering oil or bitumen-derived products in a method which is characterized by the efficient recovery of carboxylic acid and other process chemicals employed in the amphiphilic phase separation procedure.
The following examples of processes according to the invention with specific materials, flow rates, times, temperatures and other parameters should be considered to be illustrative and not restrictive of the scope of the present invention. All proportions stated in the examples are by weight unless otherwise indicated.
A solvated bitumen solution containing approximately 20 percent by weight of Kentucky bitumen, 8 percent isopropyl alcohol, 24 percent ligh-t hydrocarbon solvent such as heptane, and 48 percent tall oil derived t`atty acid solvent, such as Xtol 304, is fed to a blender 51 at a ra te of 4 .1 gpm . An alcohol/brine solution containing 68 percent isopropyl alcohol (2-propanol) and 32 percent 2500 ppm brine solution is simultaneously fed to this blender at a rate of 12.9 gpm. Under these feed conditions the product stream in line 59 from settler 55 ~ Z~ 37'~
produces 5~0 Ib/hr of a bitumen rich product containing 54 percent bitumen, 6 percent isopropyl alcohol, 38 percent heptane, and 2 percent fatty acid. The fatty acid rich solvent recycle stream would produce 1070 Ib/hr through line 89 containing 77 percent fatty acid, 7 percent bitumen, and 16 percent heptane. The concentration oE
alcohol in the alcohol/brine stream as well as the ratio of stream in line 37 to stream in lines 41 and 45 may be varied in order to procduce a variation in bitumen product stream 59. The residence times in pri mary settler 55 and in secondary settler 83 are resepctively less than 30 minutes and preferably, approximately 10 minutes.
See Table 1 below.
The procedures are the same as in Example 1, except an admixture of one or more vegetable-derived fatty acids such as soybean oil, cottonseed oil, safflower oil, palm oil, or corn oil, is used in place of all or part of the tall oil derived fatty acid. This prevents the hardening of the bitumen product that may occur in some cases because of small amounts of resin present in the tall oil derived fatty acids.
The procedures are the same as Example 1, except that the alcohol/brine stream through line 49 from tanks 31 and 35 is composed of approximately 85 percent by weight methanol and 15 percent by weight of pure water. The result is a much more fluid bitumen product containing high concentrations of fatty acid. This mode of operation is useful to provide an asphaltic blending stock for roacl pavlng. The fatty acid serves as an emulsifier in the paving asphalt .
33~
EXAl~IPLE 4 The procedures are the same as Example 1, except the alcohol/
brine stream is an admixture of at least 10 percent of two different forms of alcohol containing methanol, ethanol, l-propanol, 2-propanol, and/or butanol, to meet specified bitumen-derived product composition and characteristics. The exact admixture composition varies depending upon differences in chemical composition of the feedstock bitumen and the amount of bitumen in the feedstock stream.
E~ PLE
The procedures are the same as in a selected one of Examples, 1 to 4, except at least the bottom phase in primary settler 55 is heated to 40-50 C. resulting in a purer bitumen product in some instances .
The procedures are the same as Example 5, except the bottom phase in primary settler 108 is heated to 90-110 C. or greater to achieve a granular, solid bitumen product upon cooling. This product may be suitable for production of carbon black.
The procedures are the same as Example 1, except the brine concentration in the alcohol/brine stream is varied from 0 percent to 10 percent depending upon the bitumen feedstock properties to achieve a bitumen product containing a predetermined desired amount of fatty acid to serve as an emulsifier or for other purposes. lt is also possible in some cases to achieve desired product characteris-tics by varying the ratio of the alcohol/brine stream to the solvated bttumen stream between the ratios of 1:1 to 5:1.
337~
E~AMPLE
The procedures are the same as a selected one of Examples 1 to 7 except the residence time in primary settler 108 and secondary settler 109 is varied between 1 and 10 minutes in order to vary the composi~ion of the product bitumen stream.
EXA~PLE 9 The procedures are the same as a selected one of Examples to 8 ex cept the procedure of water overdosing as shown in FIGURE 2 is used to achieve phase equilibrium shift in secondary settler 183, and subsequent distillation is used to recover the alcohol. A dilute brine stream is discharged to salt water disposal.
The procedures are the same as Example 9 except reverse osmosis and a two distillation column system are used to recover both the alcohol and the brine, thereby substantially eliminating all discharge streams. FIGl~RE 3 shows the process flow diagram for this example, and Table 2 presents the process stream mass balance for a 336 barrel/day demonstration plant. For illustrative purposes, the product bitumen stream, line 5, was assumed to be pure bitumen in the calculations shown in Table 2.
The procedures are the same as Examples 1, 3, 4 or 5-8 except the Xtol 304 solvent is replaced by commercial oleic acid.
EXI~MPLE 12 The procedures are the same as Examples 1, 3, 4 or 5-8 except the X-tol 304 solvent is replaced by dithiobenzoic acid.
'~ Ir~
A solvated bitumen solution containing approximately 10-20 percent Fitzgerald (Oklahoma) tar sand, 5-10 percent isopropyl alcoholt 20-25 percent light hydrocarbon solvent such as heptane, and 40-60 percent acid solvent formed of an admixture of one or more of the vegetable-derived fatty acids consisting of soybean oil, cottonseed oil, safflower oil, palm oil, and corn oil, is fed to in-line blender ~1 or lSl at a rate of 4-5 gpm. An alcohol/brine solution containing 60-80 percent isopropyl alcohol (2-propanol) and 1000-3000 ppm brine solution is simultaneously fed to this blender at a rate of 10-15 gpm. The concentration of alcohol in the alcohol/
brine stream as well as the ratio of such stream to the feedstock stream may be varied in order to produce a variation in bitumen product. The residence times in primary settler 108 and in secondary settler 112 are respectively approximately 5 to 15 minutes.
EXA~IPLE 14 The procedures are the same as Example 13, except the alcohol/
brine stream is an admixture of 2 or more alcohols containing methanol, ethanol, I-propanol, 2-propanol, and/or butanol, to meet specified product composition and characteristics. The exact admixture composition is varied depending upon differences in chemical composition of the feedstock bitumen and the amount of bitumen in the feedstock.
I'he procedures are the same as in a selected one of Examples 12-14, except the bottom phase in primary settler 55 is heated to 40-50 C.
EXAI~lP~E 16 The procedures are the same as Example 13, except the brine concentration in the alcohol/brine stream is varied from 0 percent to 10 percent depending upon the bitumen feedstock properties to achieve a bitumen product containing varying amounts of fatty acid as may be desirable in some cases.
EXAl~PLE 17 ~ solvated bitumen solution containing approximately 20 percent by weight of Kentucky bitumen, 8 percent isopropyl alcohol, 24 percent light hydrocarbon solvent such as heptane, and 48 percent carboxylic acid solvent, such as dithiobenzoic acid, is fed to a blender at a rate of 4.1 gpm. An alcohol/brine solution containing 68 percent isopropyl alcohol (2-propanol) and 32 percent 2500 ppm brine solution is simultaneously fed this blender at a rate of 12.9 gpm. The concentration of alcohol in the alcohol/brine stream as well as the ratio of stream in line 37 to stream in lines 41 and 45 may be varied in order to produce a variation in bitumen product stream 59. The residence times in primary settler 55 and in secondary settler 83 are respectively less than 30 minutes and preferably, approximately 10 minutes.
The above exa~ples are illustra-tive only, and those skilled in the art will appreciate that there are numerous variations which can be employed in virtually innumerable combinations. While tar sands have been specified as bitumen source material because of their potential economic importance, other bitumen source ma-terials could be substituted, with adjustment of process parameters in some cases .
Various fatty acids have been enumerated in -the examples, but there is a wider range of carboxylic acids ( generally those having 8 to 20 carbon atoms) among which selection may be made ~.x~3t7~
based on contemporaneous price and availability or other factors.
Potential carboxylic acids for use in the process include but are not limited to the following: -mono and/or poly alkanoic acid, alkenediolic acid, alkenoic acid, alpha linoleic acid, aracadonic acid, arachidic acid, benzilic acid, bethinic acid, dithiobenzoic acid, gamma linoleic acid, hydroxyalkanoic acid, lauric acid, lignoceric acid, linoleic acid, linolenic acid, myristic acid, naphthenic acid, octadecenoic acid, oleic acid, palmitic acid, petroselaidic acid, stearic acid, tetranoic acid, thiocarboxylic acid, and/or truenoic acid.
In the same vein, alcohols for use in the process may be selected as much on the basis of current cost and availability as on other factors. Similarly, brine when referred to above is contem-plated to be a solution of water and predominantly sodium chloride, but the process is not limited to sodium chloride as the brine component, and in fact, the brine component may be omitted in some cases.
While the above described theory of operation of the process is thought to be responsible for the observed efficient separation and recovery of carboxylic acids and other advantages of the invention, the novelty and advantages of the process are not attributable to the theory presented but are due to actual results established by experimentation. Accordingly, patentability of the invention is not to be considered to be dependent on the theory presented above, although any theory presented, so far as it is known, is believed to be correct. The steps recited in the claims may in some cases be performed in a different sequence than the sequence in which they are listed, or steps may be performed concurrently.
In addition to the variations and modifications to the invention which have been described or suggested, numerous other variations or rnodifications will be apparent to those skilled in the art.
Accordingly the scope of the invention is not to be considered to 7~
be limited to the embodiments and variations described but is to be determined by re:ference to the appended claims.
~ %~3~37~:
O ~ O ~ 00U~ ~ ~ ~D
,, o ~ ~ ~ oo o o ~ ~ U~
O 1~ u; ~ O O
o u~
E~ i~ u~ ~ 0`J
. ,~ u~
.
_~o a~ o o~ oo~ O
o ~ ~ ~ o o ~ o ~ o . ~ ~ o o o o o o ~ U'~ o U~ o O ~ ~ ~ O ~ ~ o r~ o r~ r~ OD CO 0 ~a u~ ~ u~ ~ O O
_, ~ ~ ~ ,.
o o o U~ ~~ ~ o o o o ~ i o " U~
~ o U'~ ~ ~ o~ o o o o .~ ~ ,_ ~ ~ ~ ~~ ~r o~ c~
~ ~1 ~D 0 r~ r~ o ~ a:
.
~,-8 o 8 8 8 o o . o o R 9 o o o u~ u~o ~ u~ o o P~ ~ ~ U~ U~ ~ ~ ~ ~
,~ ~ ~ ~ ~ , ;
Cl ~ I~ co ooo ~ o O 00 ~ ~i ~D O ~ ~ CO O
~; C`03 ~; ~; o oo C~O~
~o o o ~ ~ ~ ~ U~ U~ o o O ~ `D O ~D ~D ~ ~ O O '.~' U~ ~ ~ ~ , oo ~;~ ~ U~ ~ ,, ,, ~ C`~
I~ ~ a~ ~ ~ O ~ ~ 0 u~
0 ~ O O O 1` ~ 0 ~3 0 U~ ~o ~ t- o ,1 ~ ,, ~ ~ ~ ~ `D 8 `D ~ ~ `D
~1 U~ U~
~ ~ o o o o o o o o o r~ r ~ ~) O~ 1~) 1~ C~ I~ ~n ~i ~ n ~ ~n r~ ~ ~ ~ ~
~ ~ D ~ ~ ~
h v~ tn u~
.
~ ~83 1~ f~C 69370--7 N l l O l l l l O
N I I O l ~ ~-1 N ~ N
N l l N ~ I ~; 01 ~
N l l N I I _ N ~p N I I$ I I ~9 ~
N I I~ I N ~D
N _ P N
N ~ ~O ~D
N _~ N
N _ _ ~ ~ I 1~ ~
1~ ~ ~N l ll I ~ l d' ~ N 1-1 . U-N ~r ~
1_~ g~ N ~O ~'I
a~ , ~ I o I u7 8 ~ , u~ I I
_ O N ~ I N ¦ ;~
O N _~
O I I l_CO I I I _ ~ l ~ r~
N ~ , ~!;
_ ~
O ~ ~ 00 1 1 1 ~
, 1
Claims (41)
1. A method for recovering crude oil from fossil fuel deposits of heavy oil or bitumen comprising the steps of:
(a) exposing an admixture containing at least one carboxylic acid to a viscous or solid crude oil source material;
(b) intimately contacting said carboxylic acid admixture with respect to the source material to produce a solvated crude oil mixture of reduced viscosity;
(c) blending the solvated crude oil mixture with an alcohol-water solution to produce an amphiphilic phase separation of the resulting mixture;
(d) gravity separating the resulting mixture in a settling chamber by extracting an alcohol-water-acid phase from the top of said chamber;
(e) distilling said alcohol-water-acid phase to at least partially separate said carboxylic acid from said alcohol-water solution;
(f) further gravity separating the acid component output from said distilling step to produce recovered carboxylic acid with reduced water and alcohol content;
(g) recycling the recovered carboxylic acid into step (a); and (h) recycling recovered alcohol-water solution into step (c).
(a) exposing an admixture containing at least one carboxylic acid to a viscous or solid crude oil source material;
(b) intimately contacting said carboxylic acid admixture with respect to the source material to produce a solvated crude oil mixture of reduced viscosity;
(c) blending the solvated crude oil mixture with an alcohol-water solution to produce an amphiphilic phase separation of the resulting mixture;
(d) gravity separating the resulting mixture in a settling chamber by extracting an alcohol-water-acid phase from the top of said chamber;
(e) distilling said alcohol-water-acid phase to at least partially separate said carboxylic acid from said alcohol-water solution;
(f) further gravity separating the acid component output from said distilling step to produce recovered carboxylic acid with reduced water and alcohol content;
(g) recycling the recovered carboxylic acid into step (a); and (h) recycling recovered alcohol-water solution into step (c).
2. The method as recited in claim 1 wherein said carboxylic acid admixture is selected from the group consisting of: lauric acid; myristic acid; palmitic acid; stearic acid; arachidic acid;
bethinic acid; lignoceric acid; mono and/or poly alkanoic acid;
hydroxyalkanoic acid; alkenediolic acid; alkenoic acids, linoleic acid; truenoic acids; and tetranoic acids.
bethinic acid; lignoceric acid; mono and/or poly alkanoic acid;
hydroxyalkanoic acid; alkenediolic acid; alkenoic acids, linoleic acid; truenoic acids; and tetranoic acids.
3. The method as recited in claim 2 wherein said alkanoic acids are selected from the group consisting of oleic acid, petroselaidic acid and octadecenoic acid.
4. The method as recited in claim 2 wherein said truenoic acids are selected from the group consisting of alpha linoleic and gammalinoleic acid.
5. The method as recited in claim 2 wherein said tetranoic acids include aracadonic acid.
6. The method as recited in claim 1 wherein said alcohol-water solution of step (c) has a brine component.
7. The method as recited in claim 6 wherein the brine component comprises sodium chloride.
8. The method as recited in claim 1 wherein said carboxylic admixture also contains alkane, lower alcohols, and aromatic solvents selected from the group consisting of pentane, hexane, heptane, toluene, benzene, methanol, ethanol, isopropanol, methylene chloride, and light petroleum distillates.
9. The method as recited in claim 1 wherein said carboxylic acid admixture consists of at least one carboxylic acid with molecules having between 8 and 20 carbon atoms.
l.''`
l.''`
10. A method for recovering crude oil from fossil fuel deposits of heavy oil or bitumen comprising the steps of:
(a) exposing an admixture containing at least one carboxylic acid having 8 to 20 carbon atoms to a viscous or solid crude oil source material;
(b) contacting said carboxylic acid admixture with respect to the source material for a time sufficient to produce a solvated crude oil mixture of reduced viscosity;
(c) blending the solvated crude oil mixture of step (b) with an alcohol-water solution to produce phase separation of the resulting mixture;
(d) gravity separating the resulting liquid of step (c) by extracting an alcohol-water-acid phase of lesser density from the liquid;
(e) separating said carboxylic acid from said alcohol-water-acid solution;
(f) recycling the recovered carboxylic acid into step (a); and (g) recycling recovered alcohol-water solution into step (c).
(a) exposing an admixture containing at least one carboxylic acid having 8 to 20 carbon atoms to a viscous or solid crude oil source material;
(b) contacting said carboxylic acid admixture with respect to the source material for a time sufficient to produce a solvated crude oil mixture of reduced viscosity;
(c) blending the solvated crude oil mixture of step (b) with an alcohol-water solution to produce phase separation of the resulting mixture;
(d) gravity separating the resulting liquid of step (c) by extracting an alcohol-water-acid phase of lesser density from the liquid;
(e) separating said carboxylic acid from said alcohol-water-acid solution;
(f) recycling the recovered carboxylic acid into step (a); and (g) recycling recovered alcohol-water solution into step (c).
11. The method as recited in claim 10 wherein said alcohol-water solution of step (c) has a brine component.
12. The method as recited in claim 11 wherein the brine component comprises sodium chloride.
13. The method as recited in claim 10 wherein said carboxylic acid is selected from the group consisting of benzilic acid, dithiobenzoic acid, linoleic acid, linolenic acid, myristic acid, naphthenic acid, oleic acid, palmitic acid, stearic acid, and thiocarboxylic acids.
14. The method as recited in claim 10 wherein said alochol is predominately methanol.
15. The method as recited in claim 10 wherein said alcohol is predominately isopropanol.
16. The method as recited in claim 10 further including a step of mixing a light hydrocarbon with said carboxylic acid admixture prior to step (c).
17. The method as recited in claim 16 wherein said light hydrocarbon is heptane.
18. The method as recited in claim 10 further including the step of heating the solvated crude oil mixture of step (b) to a temperature of at least 40 degrees Celsius.
19. The method as recited in claim 10 further including the step of decreasing the concentration of alcohol in said alcohol-water solution before step (e).
20. The method as recited in claim 19 further including the step of heating the solvated crude oil mixture of step (b) to a temperature of at least 40 degrees Celsius.
21. The method as recited in claim 10 wherein step (e) is accomplished at least in part by injecting process water to overdose the solution and shift the phase equilibrium to enable gravity separation of said acid.
22. The method as recited in claim 21 wherein said carboxylic acid admixture is selected from the group consisting of: lauric acid; myristic acid; palmitic acid; stearic acid, arachidic acid; bethinic acid; lignoceric acid; mono and/or poly alkanoic acid; hydroxyalkanoic acid; alkenediolic acid; alkenoic acids; linoleic acid; truenoic acids; and tetranoic acids.
23. The method as recited in claim 22 wherein said truenoic acids are selected from the group consisting of alpha linoleic and gamma linoleic acid.
24. The method as recited in claim 22 wherein said tetranoic acids include aracadonic acid.
25. The method as recited in claim 10 wherein said alcohol water solution of step (c) has a brine component.
26. The method as recited in claim 25 wherein the brine component comprises sodium chloride.
27. The method as recited in claim 10 wherein said carboxylic acid consists of at least two carboxylic acids each with molecules having between 8 and 20 atoms.
28. A method for recovering oil from viscous or solid oil source material comprising the steps of:
(a) exposing an admixture containing at least one of the carboxylic acids to said viscous or solid oil source material to produce a solvated oil mixture of reduced viscosity;
(b) blending the solvated crude oil mixture with an alcohol to produce phase separation of the resulting mixture;
(c) separating the resulting mixture from step (b) into different density components including one alcohol-acid component;
(d) further separating an acid component from said alcohol-acid component to produce recovered carboxylic acid with reduced alcohol content;
(e) recycling the recovered carboxylic acid into step (a); and (f) recycling recovered alcohol solution into step (b).
(a) exposing an admixture containing at least one of the carboxylic acids to said viscous or solid oil source material to produce a solvated oil mixture of reduced viscosity;
(b) blending the solvated crude oil mixture with an alcohol to produce phase separation of the resulting mixture;
(c) separating the resulting mixture from step (b) into different density components including one alcohol-acid component;
(d) further separating an acid component from said alcohol-acid component to produce recovered carboxylic acid with reduced alcohol content;
(e) recycling the recovered carboxylic acid into step (a); and (f) recycling recovered alcohol solution into step (b).
29. The method as recited in claim 28 wherein said carboxylic acid is selected from the group consisting of myristic acid; palmitic acid; stearic acid; linoleic acid; and oleic acid.
30. The method as recited in claim 28 wherein said carboxylic acids are alkanoic acids selected from the group consisting of oleic acid, petroselaidic acid and octadecenoic acid.
31. The method as recited in claim 28 wherein said carboxylic acids are truenoic acids selected from the group consisting of alpha linoleic acid and gammalinoleic acid.
32. The method as recited in claim 28 wherein said carboxylic acids include aracadonic acid.
33. The method as recited in claim 28 wherein said alcohol-water solution of step (c) has a brine component.
34. The method as recited in claim 33 wherein the brine component comprises sodium chloride.
35. The method as recited in claim 28 wherein said carboxylic admixture also contains alkane, lower alcohols, and aromatic solvents selected from the group consisting of pentane, hexane, heptane, toluene, benzene, methanol, ethanol, isopropanol, methylene chloride, and light petroleum distillates.
36. The method as recited in claim 28 wherein said carboxylic acid admixture consists of at least one carboxylic acid with molecules having between 8 and 20 atoms.
37. The method as recited in claim 28 wherein said carboxylic acid is selected from the group consisting of benzilic acid/ dithiobenzoic acid, linoleic acid, linolenic acid, myristic acid, naphthenic acid, oleic acid, palmitic acid, stearic acid, and thiocarboxylic acids.
38. The method as recited in claim 28 wherein said alcohol is predominantly isopropanol.
39. The method as recited in claim 28 further including the step of heating the solvated oil mixture of step (a) to a temperature of at least 40 degrees Celsius.
40. The method as recited in claim 28 further including the step of decreasing the concentration of alcohol in said alcohol-water solution before step (d).
41. The method as recited in claim 23 wherein step (d) is accomplished at least in part by injecting process water to overdose the solution and shift the phase equilibrium to enable gravity separation of said acid.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/932,688 US4673484A (en) | 1986-11-19 | 1986-11-19 | Amphiphilic phase behavior separation of carboxylic acids/hydrocarbon mixtures in recovery of oil from tar sands or the like |
US932,688 | 1986-11-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1288372C true CA1288372C (en) | 1991-09-03 |
Family
ID=25462734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000551228A Expired - Fee Related CA1288372C (en) | 1986-11-19 | 1987-11-06 | Amphiphilic phase behavior separation of carboxylic acids/hydrocarbon mixtures in recovery of oil from tar sands or the like |
Country Status (2)
Country | Link |
---|---|
US (1) | US4673484A (en) |
CA (1) | CA1288372C (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5156686A (en) * | 1990-11-30 | 1992-10-20 | Union Oil Company Of California | Separation of oils from solids |
US5620588A (en) * | 1991-02-11 | 1997-04-15 | Ackerson; Michael D. | Petroleum-wax separation |
US5196116A (en) * | 1991-02-11 | 1993-03-23 | University Of Arkansas | Process for petroleum - wax separation at or above room temperature |
US5474668A (en) * | 1991-02-11 | 1995-12-12 | University Of Arkansas | Petroleum-wax separation |
US6536523B1 (en) | 1997-01-14 | 2003-03-25 | Aqua Pure Ventures Inc. | Water treatment process for thermal heavy oil recovery |
US6372123B1 (en) | 2000-06-26 | 2002-04-16 | Colt Engineering Corporation | Method of removing water and contaminants from crude oil containing same |
CA2351148C (en) * | 2001-06-21 | 2008-07-29 | John Nenniger | Method and apparatus for stimulating heavy oil production |
US7691259B2 (en) * | 2006-03-03 | 2010-04-06 | M-I L.L.C. | Separation of tar from sand |
CA2549614C (en) * | 2006-06-07 | 2014-11-25 | N-Solv Corporation | Methods and apparatuses for sagd hydrocarbon production |
CA2552482C (en) * | 2006-07-19 | 2015-02-24 | N-Solv Corporation | Methods and apparatuses for enhanced in situ hydrocarbon production |
ES2340452B1 (en) * | 2007-06-05 | 2011-05-19 | Sadyt | DEVICE AND PROCEDURE FOR DESALATION OF SALMUERAS PROCEDURES DEDESALADORAS DE SOLUBRUAS WATER WITH A SOLVENT MISCIBLE WITH WATER. |
CN102712848B (en) | 2009-08-17 | 2016-01-13 | 布拉克卡培都能源科技有限公司 | Oil-sand extracts |
US20110147276A1 (en) * | 2009-12-23 | 2011-06-23 | General Electric Company | Method for recovering bitumen from oil sand |
US10012064B2 (en) | 2015-04-09 | 2018-07-03 | Highlands Natural Resources, Plc | Gas diverter for well and reservoir stimulation |
US10344204B2 (en) | 2015-04-09 | 2019-07-09 | Diversion Technologies, LLC | Gas diverter for well and reservoir stimulation |
US9926493B2 (en) | 2016-04-22 | 2018-03-27 | Dolly Nicholas | Process for the removal of the heavy oil from tar sand (either oil/hydrocarbon wet or water wet deposits) and the cleaning up of the effluent |
US10982520B2 (en) | 2016-04-27 | 2021-04-20 | Highland Natural Resources, PLC | Gas diverter for well and reservoir stimulation |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3006411A (en) * | 1961-10-31 | Surfactant water | ||
US3373809A (en) * | 1965-11-15 | 1968-03-19 | Exxon Production Research Co | Microemulsion oil recovery process |
US3691211A (en) * | 1970-12-07 | 1972-09-12 | Procter & Gamble | Process for preparing sterols from tall oil pitch |
US4192651A (en) * | 1977-11-21 | 1980-03-11 | The Keller Corporation | Method of producing pulverulent carbonaceous fuel |
US4213500A (en) * | 1978-06-26 | 1980-07-22 | Texaco Inc. | Oil recovery process: injection of fatty alcohol followed by soap |
US4222849A (en) * | 1979-07-05 | 1980-09-16 | Kunitoshi Shimizu | Process of liquefaction of coal |
US4388170A (en) * | 1979-12-04 | 1983-06-14 | Klaus Schmid | Process for producing lower-molecular-weight hydrocarbons from higher molecular-weight hydrocarbons and auxiliary agent therefor |
US4311561A (en) * | 1980-04-02 | 1982-01-19 | Tarco Incorporated | Apparatus for extracting bitumen from tar sand |
US4338185A (en) * | 1981-01-02 | 1982-07-06 | Noelle Calvin D | Recovery of oil from oil sands |
US4480691A (en) * | 1982-09-29 | 1984-11-06 | Herter George L | Recycled fatty acid crude petroleum recovery process |
US4572292A (en) * | 1984-04-04 | 1986-02-25 | Phillips Petroleum Company | Enhanced oil recovery |
-
1986
- 1986-11-19 US US06/932,688 patent/US4673484A/en not_active Expired - Fee Related
-
1987
- 1987-11-06 CA CA000551228A patent/CA1288372C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US4673484A (en) | 1987-06-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1288372C (en) | Amphiphilic phase behavior separation of carboxylic acids/hydrocarbon mixtures in recovery of oil from tar sands or the like | |
US3491835A (en) | Recovering,desalting,and transporting heavy crude oils | |
US4968412A (en) | Solvent and water/surfactant process for removal of bitumen from tar sands contaminated with clay | |
US4046668A (en) | Double solvent extraction of organic constituents from tar sands | |
US4512872A (en) | Process for extracting bitumen from tar sands | |
US8685234B2 (en) | Extraction of hydrocarbons from hydrocarbon-containing materials and/or processing of hydrocarbon-containing materials | |
US4389300A (en) | Solvent extraction method | |
US3442332A (en) | Combination methods involving the making of gaseous carbon dioxide and its use in crude oil recovery | |
AU2009341831A1 (en) | Extraction of hydrocarbons from hydrocarbon-containing materials and/or processing of hydrocarbon-containing materials | |
US4806231A (en) | Method for desalting crude oil | |
US4401551A (en) | Solvent extraction method | |
WO1991010040A1 (en) | Process for in-situ enrichment of gas used in miscible flooding | |
US4836935A (en) | Oil removal from waterflooding injection water | |
CA2777966C (en) | Solvent injection plant for enhanced oil recovery and method of operating same | |
US4123357A (en) | Recovering oil from emulsion by stirring, heating, and settling | |
US2139595A (en) | Method for dissolving paraffing and wax | |
CA1156583A (en) | Extraction of oil using amides | |
US3267998A (en) | Separation process | |
US4457827A (en) | Process for extracting bitumen from tar sands | |
US2677666A (en) | Process for removing contaminants from crude oils | |
US4181177A (en) | Controlling shale oil pour point | |
US3547803A (en) | Recovery of oil from bituminous sands | |
US5152886A (en) | Method for improving heavy crude oils by reducing the asphaltene content of crude oils and oil-containing tar sands | |
CA2165865C (en) | Process for deasphalting bitumen | |
CN106966559A (en) | A kind of oil-sludge treatment dispersant and its preparation method and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKLA | Lapsed |